Process for manufacturing alkylaluminum compounds

ABSTRACT

ALUMINUM OR ITS ALLOY IS ACTIVATED BY HEATING ALUMINUM OR ITS ALLOY AT 70 -200*C. IN THE PRESENCE OF AN ACTIVATING AGENT COMPRISING (1) A COMPOUND REPRESENTED BY THE GENERAL FORMULA R2AIX, WHEREIN R REPRESENTS AN ALKYL, ARYL, ARALKYL OR ALKARYL GROUP AND X REPRESENTS A HYDROGEN ATOM, AN ALKYL, ARYL, ARALKYL,ALKARYL, ALKOXY, AROXY, ARALKOXY OR ALKAROXY GROUP OF A HALOGEN ATOM. (2) A METAL OF GROUPS IA AND IIA OF THE PERIODIC TABLE OR ITS COMPOUND, AND (3) METALLIC COOPER OR ITS COMPOUND.

Un ed Stat sPat O 3,770,789 PROCESS FOR MANUFACTURIN ALKYLALUMINUM COMPOUNDS Eiichi Ichiki, .Kazuo Iida, Atsuro Matsui, and Hidekimi Kadokura, Niihama, Japan, assignors to Sumitomo Chemical Company, Limited, Osaka, Japan No Drawing. Filed Feb. 16, 1971, Ser. No. 115,800 Claims priority, application Japan, Feb. 21, 1970,

45/14,944 Int. Cl. C071? /06 US. Cl. 260-448 A 11 Claims This invention relates to a process for activating aluminum or its alloy used in the preparation of alkylalu minium compounds, and particularly to a process for activating aluminum or its alloy used in the preparation of alkylaluminums through a reaction of aluminum, alkylaluminum compounds and hydrogen or through a reaction of aluminum, alkylaluminum compounds, hydrogen and olefins.

The reaction for directly synthesizing alkylaluminum compounds through a reaction of aluminum, alkylaluminum compounds and hydrogen or through a reaction of aluminum, alkylaluminum compounds, hydrogen and olefins is well known (for example, Japanese Pat. No. 236,- 648).

However, said reaction has such a disadvantage that the reaction rate is generally low, because the surface of aluminum is covered with an oxide film capable of repressing the reaction, though the aluminum itself is a very reactive metal.

Heretofore, a process for activating aluminum by adding to the alkylaluminum compound a small amount of alkali metal, alkaline earth metal or their oxides, hydroxides, etc. and heating aluminum under pressure by hydrogen is known (U.S. Pat. No. 2,892,738), but said prior art process has such a disadvantage that the activation time is prolonged. Further, a process for activation by heating aluminum or its alloy in the presence of lithium, sodium, potassium, magnesium, calcium, aluminum and others having an alkoxy group or aroxy group is known (Japanese Pat. No. 487,801). Said prior art process is preferable, because the activation time can be considerably shortened, as compared with said other prior art processes.

As a result of various studies on processes for activating aluminum or its alloy used in the synthesis of alkylaluminum compounds, the present inventors have found that, when metallic copper or a copper compound is used together with some specific activating agent, a considerably excellent activation efiect can be attained, as compared with the effect attained by any one of said well known processes for activation, though the metallic copper or the copper compound alone has no activation effect at all.

That is to say, an object of the present invention is to provide a process for activating aluminum or its alloy, where an alkylaluminum compound is prepared by subjecting Patented Nov. 6, 1973 aluminum orits alloy, an alkylaluminum compound and hydrogen, or aluminum or its alloy, an alkylaluminum compound, hydrogen and an olefin, to reaction, which comprises activating the raw material aluminum or its alloy in the presence of an activating agent comprising (1) a compound represented by the general formula, R AlX, wherein R represents an alkyl, aryl, aralkyl or alkaryl group, X represents a hydrogen atom, an alkyl, aryl, aralkyl, alkaryl, alkoxy, aroxy, aralkoxy or alkaroxy group or 'a halogen atom, (2) a metal selected from the Groups Ia and Ila of the Periodic Table or its compound, and (3) a metallic copper or its compound at a temperature of -200'C.

Aluminum or its alloy can be used in the present invention as the raw material, irrespective of its shape or composition. Usually, pulverized or atomized aluminum powders, cutting aluminum pieces by lathe and drilling machine or aluminum drilling waste, etc. can be used. Further, an aluminum alloy containing silicon, iron, titanium, magnesium or the like can be used as an alloy.

The activating agent used in the present invention comprises (l) a compound represented by the general formula, R AlX, wherein R and X have the same meaning as defined above, (2) a metal selected from the Groups Ia and Ila of the Periodic Table, or its compound, and (3) a metallic copper or its compound. The compounds represented by the general formula, R AlX, as the first component, wherein R and X have the same meaning as defined above, include such trialkylaluminums, dialkylaluminum hydrides or arylaluminum compounds having 2 to 20 carbon atoms as triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, dioctylaluminum hydride, diethylphenylaluminum, diethyl-p-tolylaluminum, or such alkylaluminum halides having 2 to 20 carbon atoms as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, or dipropylaluminum bromide; or such alkoxides, aroxides, alkaroxides or aralkoxides of alkylaluminum or arylaluminum having an alkyl group or an aryl group having 2 to 20 carbon atoms as diethylaluminum ethoxide, diisobutylaluminum butoxide, dioctylaluminum octoxide, diethylaluminum phenoxide, diethylaluminum 2-phenylpropoxide, diethylaluminum ptolyloxide or diphenylaluminum ethoxide. These compounds can be used alone or in a proper combination.

Further, the metal selected from the Groups In and Ila of the Periodic Table or its compound as the second component includes such metals as lithium, sodium, potassium, or calcium, such compounds as hydrides, hydroxides, carbonates, bicarbonates, oxides, chelate compounds or organic acid salts of lithium, sodium, potassium, magnesium, calcium, barium, etc., such compounds of lithium, sodium, potassium, magnesium, or calcium having, in one molecule, at least one alkoxy or aroxy group having 2-20 carbon atoms in one group, as ethoxysodium, isopropoxylithium, dinormalpropoxycalcium, tertiarybutoxypostassium, or dinormalbutoxymagnesium, etc. These compounds can be used alone or in a proper combination.

The metallic copper or copper compounds as the third component includes such copper compounds a cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cuprous oxide, cupric oxide, cupric sulfate, cupric nitrate, cupric hydroxide, cuprous cyanide, copper acetate, copper acetyl-acetonate, copper formate, copper naphthenate, copper octylate, copper oleate, copper stearate, copper oxalate, disodium copper ethylenediaminetetraacetate, etc. These compounds can be used alone or in a proper combination.

The present invention is characterized by using an activating agent comprising said three components, and in that case, the activation effect of an activating agent comprising said three components is higher than the effect of the activating agent comprising two of said three components.

The following procedure is suitable for activating the alloy and the present activating agent or further an organic solvent are charged into a reactor, and then an alkylaluminum compound (the alkylaluminum compound used as the first component of the present activating agent can aluminum or its alloy: that is, aluminum or its alloy is be used as a substitute because all the alkylaluminum comheat-treated in the presence of the present activating agent pounds have an equivalent effect), and hydrogen or further comprising said three components. The activation temperaan olefin are supplied to the reactor. The activation and ture generally 70-200 C., particularly 100-170 C. the direct synthetic reaction of alkylalurninum compounds If the activation temperature exceeds said upper limit, can be carried out in parallel by heating the reactor to that is, 200 C., a portion of the activating agent under- 70-200 C. The above-mentioned process is only for an goes thermal decomposition, and the activation effect is illustrative purpose and can be modified in various manlowered. If the activation temperature is lower than said ners. lower limit, that is, 70 C., the activation time is pro- It has been not clear yet whey the present activating longed and therefore the lower activation temperature is agent has a considerably excellent effect, as compared not f bl with the well-known activating agent, but it is a surpris- The suitable amounts of the respective components of ing fact that the metallic copper or its compound, which the activating agent are given below, on the basis of the has no activation effect at all when it is used alone or in aluminum or its alloy to be activated: it is desirable that a simple combination of other well known activating agent, the first component is 5% by weight or more, the second can have such a considerably excellent activation efi'ect component is 0.001% by weight or more and the third when combined with the specific components as defined component is 0.000l% by weight or more. These comabove. By using the present activating agent, the activaponents of the activating agent can be added to the retion time can be considerably shortened, and the fluctuaaction system together after mixing these three comtion in the activation effect encountered in the convenponents in advance or separately. tional activating agent can be overcome. Therefore, the

The activation time depends upon the raw material present invention has an industrially important value. aluminum or its alloy and thus cannot be exactly defined, Now, the present invention will be explained, referring but satisfactory activation can be attained usually for to examples, but will not be restricted thereto. more than 0.2 hour. It is desirable to carry out the activation in such a state that the aluminum or its alloy is EXAMPLE 1 sufficienfiy Wet with the activating agent 27 g. of aluminum lathe scraps and an activating agent The activation can be also carried out in the presence as Shown i T bl 1 ware h d i an autoclave of such an Organic Solvent as hexane, P benlene, having a 1-1. capacity replaced with a nitrogen gas and toluene, y acetone, diphenylether, p py heated to 150 C. with stirring under pressure with hydrobutylether, cyclohexane, etc. Further, the activation can gen and kept at that temperature for two hours, whereby be carried out more preferably under pressure with hydroaluminum was activated. After the activation, the autogen. In the activation, other activating agent generally well clave was cooled to room temperature and the activating known as the activating agent for aluminum or its alloy agent was taken out of the autoclave. can be used. Then, 100 g. of triisobutylaluminum and 130 g. of iso- The activated aluminum or its alloy obtained accord- 4O butylene were charged into the autoclave and the autoing to said procedure can be used as a raw material for clave was heated to 140 C. with stirring, and the reaction the well-known production of dialkylalurninum hydride or pressure was kept at 100 kg./cm. by supplying hydrogen trialkylaluminum from the alkylaluminum compound, thereto. The reaction was continued for 6 hours. After the aluminum or its alloy and hydrogen, or from the alkylcompletion of the reaction, the autoclave was cooled to aluminum, aluminum or its alloy, hydrogen and olefin. room temperature and the content was taken out of the Generally, the reaction of the alkylaluminum comauoclave after the gas was vented from the autoclave. pound, aluminum or its alloy and hydrogen, or th reac- The weight of aluminum residue was weighed to detion of the alkylaluminum compound, aluminum or its termine as the conversion of aluminum. The result is alloy, hydrogen and the olefin is carried out at a temshown as the conversion in the table. perature of -200 C., particularly l00150 C. and 50 As is clear from the table, the conversion was far better under a pressure of l03 00 kg./cm. particularly 50-200 when the present activating agent was used as in Test Run kg./cm. However, in the present invention, it is possible N 5 12, h h propelbi i of two to carry out said two-step process in the following one pouents of the constituents of the present activating agent step process. That is to say, first of all, aluminum or its were used as in Test Run No. .l-4.

TABLE Activating agent Test Conversion run Amount Amount Amount of alumi- No. added, g (2) 14 added, g. (3) 3 added, g. num, percent Remarks 1 Triisobutylaluminum Ethoxypotassium 0.50 30.2 Comparative 2 Diisobutyl aluminum bromide. 10o Tert-Butoxy potassium- 0.50 28.5 ia i 3 Triisobutyl aluminum 100 Cupn'e chloride- 0 040 3.0 Do. 4. 4 Et-hoxysodium 0.50 d 0.040 15.8 Do. 5 Triethylalumiuum 100 Metallic sodium... 0.25 do 0. 040 56.4 G Diethylaluminum hydride 100 Calcium hydride 0.50 ..do 0. 040 49.1 7 Tripropylaluminum 100 Diet-hoxymagnesium 0.70 Metallic eoppen- 0 020 50.7 8 Triisobutyl aluminum 100 Ethoxysodinm 0.50 Cupric oxide. .025 60.0 9 Diisobutyl aluminum hydride 100 Lithium hydride 0.20 Copperh t 0.310 52.3 10-.- 'Irioctylaluminum 100 Potassium chloride 0.50 cgggii a i' fi' 0 073 57.2 11 Diethylaluminmn chloride 100 Calcium acetate .z. 0.50 C p i'igfiii ateu 0 042 47.3 12 Dlethylaluminum phenoxide 100 Sodium carbonate 0.50 Copper stearate. 0 100 54.5

1 Alkylalmninum compound.

9 Metal of Groups In and Ha of the Periodic Table or its compound. Metallic copper or its compound.

Xylene 100 g.

EXAMPLE 2 33.8 g. of lathe scraps of an alloy consisting of 80% by weight of aluminum and 20% by weight of silicon and an activating agent consisting of 100 g. of tn'isob-utylaluminum, 0.5 g. of butoxypotassium and 0.040 g. of cupric chloride were charged into an autoclave having a 1-1. capacity replaced with a nitrogen gas, and the autoclave was kept at 130 C. for 2 hours with stirring under pressure with hydrogen, whereby aluminum alloy was activated. After the activation, the content was cooled to room temperature and the activating agent was taken out of the autoclave. Then, 60 g. of triisobutylaluminum and 130 g. of isobutylene were charged into the autoclave, and the autoclave was heated to 120 C. with stirring, and the reaction pressure was kept to 100 kg./ cm. by supplying hydrogen thereto. The reaction was continued for 4 hours. After the completion of the reaction, the autoclave was cooled to room temperature and the content was taken out of the autoclave after the gas was vented from the autoclave. Then, the weight of metal residue was weighed to determine the conversion of aluminum. As a result, the conversion was 82.0%.

For comparison, the reaction was carried out in the same manner as above, except that 100 g. of triisobutylaluminum and 0.8 g. of butoxypotassium were used as the activating agent. As a result, the conversion was 40.5%.

EXAMPLE 3 27 g. of aluminum powders, an activating agent consisting of 100 g. of diisobutylaluminum, 0.30 g. of sodium hydride and 0.10 g. of copper naphthenate, and 130 g. of isobutylene were charged into an autoclave having a 1-1. capacity replaced with a nitrogen gas, and the autoclave was heated to 150 C. with stirring. The reaction pressure was maintained at 100 kg./cm. by supplying hydrogen thereto and the reaction was continued for 6 hours. After the completion of the reaction, the autoclave was cooled to room temperature, and the content was taken out of the autoclave after the gas was vented out of the autoclave. The weight ofthe aluminum residue was weighed to determine the conversion of aluminum. As a result, the conversion was 95%.

For comparison, the reaction was carried out in the same manner as above, except that 100 g. of triisobutylaluminum and 0.30 g. of sodium hydride were used as the activating agent. As a result, the conversion was 67%.

What is claimed is:

1. A process for activating aluminum or its alloy, which comprises heating aluminum or its alloy at a temperature of 70200 C. in the presence of an activating agent comprising (1) at least 5% by weight of a com.- pound represented by the general formula, R AlX, as the first component, wherein R represents an alkyl, aryl, aralkyl or alkaryl group and X represents a hydrogen atom, an alkyl, aryl, aralkyl, alkaryl, alkoxy, aroxy, aralkoxy or alkaroxy group or a halogen atom, (2) at least 0.001% by weight of a metal selected from the group consisting of lithium, sodium, potassium and calcium; or the compound selected from the group consisting of hydrides, hydroxides, carbonates, bicarbonates, or oxides of lithium, sodium, potassium, magnesium, calcium or barium; or potassium chloride; or calcium acetate or the compound of lithium, sodium, potassium, magnesium or calcium having, in one molecule, at least one alkoxy or aroxy group having 2 to 20 carbon atoms in one group as the second component, and (3) at least 0.0001% by weight of a metallic copper or its compound selected from the group consisting of halides, oxides, sulfates, nitrates, hydroxides, or cyanides, or a copper compound selected from the group consisting of copper acetate, copper acetylacetonate, copper formate, copper naphthenate, copper octylate, copper oleate, copper stearate, copper oxalate and disodium copper ethylenediarninetetraacetate as the third component on the basis of the aluminum or its alloy to be activated.

I 2. A process according to claim 1, wherein the heating is carried out at 1'00170 C.

3. A process according to claim 1, wherein the heating is carried out for at least 0.2 hours.

4. A process according to claim 1, wherein the activation is carried out in the presence of an organic solvent.

5. A process according to claim 4, wherein the organic solvent is hexane, pentane, benzene, toluene, xylene, acetone, diphenylether, dipropylether, dibutylether or cyclohexane.

6. A process according to claim 1, wherein the activation is carried out under pressure with hydrogen.

7. A process according to claim 1, wherein the aluminum is pulverized or atomized aluminum powders, cutting aluminum pieces by lat-he and drilling machine or aluminum drilling waste.

8. A process according to claim 1, wherein the alloy is an aluminum alloy with silicon, iron, titanium or magnesium.

9. A process according to claim 1, wherein the first component is such trialkylaluminums and dialkylaluminum hydrides having 2 to 20 carbon atoms as triethylaluminum, triisobutylaluminum, trioctylaluminum, diisobutylaluminum hydride, or dioctylaluminum hydride, or dialkylaluminum hydride, or such alkylaluminum halide having 2 to 20 carbon atoms as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride or dipropylaluminum bromide, or such alkylaluminum alkoxides or alkylaluminum aroxides having an alkyl group or an aryl group having 2 to 20 carbon atoms as diethylaluminum ethoxide, diisobutylaluminum butoxide, dioctylaluminum octoxide, or diethylaluminum phenoxide.

'10. A process according to claim 1, wherein the third component is selected from the group consisting of cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cuprous oxide, cupric oxide, cupric sulfate, cupric nitrate, cupric hydroxide, cuprous cyanide, copper acetate, copper acetylacetonate, copper formate, copper naphthenate, copper octylate, copper oleate, copper stearate, copper oxalate and disodium copper ethylenediaminetetraacetate.

11. A process for manufacturing alkylaluminum compounds, which comprises reacting a member selected fromthe group consisting of aluminum and aluminum alloys with hydrogen, and a member selected from the group consisting of trialkylaluminum, dialkylaluminum hydride, alkylaluminum halide and alkylaluminum alkoxide with or without an olefin in the presence of an activating agent comprising (1) at least 5% by weight of a compound represented by the general formula, R AIX, as the first component, wherein R represents an alkyl, aryl, aralkyl or alkaryl group and X represents a hydrogen atom, an alkyl, aryl, aralkyl, alkoxy, aroxy, aralkoxy alkaryl or alkaroxy group or a halogen atom, (2) at least 0.001% by weight of a metal selected from the group consisting of lithium, sodium, potassium and calcium; or the compound selected from the group consisting of hydrides, hydroxides, carbonates, bicarbonates, or oxides of lithium, sodium, potassium, magnesium, calcium or barium; or potassium chloride; or calcium acetate of the compound of lithium, sodium, potassium, magnesium or calcium having, in one molecule, at least one alkoxy or aroxy group having 2 to 20 carbon atoms in one group as the second component, and (3) at least 0.0001% by weight of a metallic copper or its compound selected from the group consisting of halides, oxides, sulfates, nitrates, hydroxides, or cyanides, or a copper compound selected from the group consisting of copper acetate, copper acetylacetonate, copper formate, copper naphthenate, copper octylate, copper stearate, copper oxalate and disodium copper ethylenediamine tetraacetate as the third 7 8 component on the basis of the aluminum or its alloy to 3,393,217 7/1968 Ichiki et a1. 260-448 A be activated. 7 3,402,190 9/ 19968 Toyoshima et ai. 260-448 A References Cited UNITED STATES PATENTS 3,576,832 4/1971 Becker zso -44s A 5 US. Cl. X.R. 3,381,024 4/1968 Toyoshima et a1. 260-448 A 7568 HELEN M. S. SNEED, Primary Examiner 

